Patent GB-740563-A (GB)
Title: Process for the production of basic thiophosphoric or dithiophosphoric acid esters
IPC: A01N57/10
Filed: 1953-03-30
Abstract: The invention comprises as new compounds basic thiophosphoric and dithiophosphoric acid esters having the formula <FORM:0740563/IV(a)/1> wherein R1 and R2 each represent an alkyl radical, X represents sulphur or oxygen, alkylene represents an alkylene radical containing from 2 to 4 carbon atoms and Am represents a dialkylamino, alkyleneimino or morpholino radical.  The esters may be prepared by reacting an alkali metal or ammonium salt of a thiophosphoric or dithiophosphoric acid diester of the formula (R1O)(R2O).PS(X.H) with a haloalkyl amine of the formula Y-alkylene-Am, wherein R1, R2, X, alkylene and Am are as defined above and Y is a chlorine or bromine atom. Instead of reacting the salts of thiophosphoric or dithiophosphoric acid diesters with the haloalkyl amines, the thiophosphoric or dithiophosphoric acid diesters themselves can be used in the presence of acid binding agents such as sodium or potassium carbonate, pyridine, or dimethyl aniline.  The products may also be obtained by reacting a thiophosphoric acid diester halide of the formula (R1O)(R2O).  PS(Y) with an alkali metal salt of a primary or secondary basic alcohol or mercaptan of the formula H-X-alkylene-Am, wherein R1, R2, X, Am, Y and alkylene are as defined above.  Also the free basic alcohols or mercaptans can be used in the presence of acid binding agents instead of the alkali metal salts.  The reactions may be carried out in the presence of an inert solvent, e.g. a low molecular aliphatic alcohol or ketone such as acetone, a carboxylic acid ester or a benzene hydrocarbon.  The reaction is generally effected at 20-100 DEG  C. Specified starting materials are on the one hand: dimethyl-, diethyl-, diisopropyl-, and di-n-butylthio or dithio-phosphoric acid ester or the chlorides or bromides of these thiophosphoric acid diesters (dialkoxythiophosphoryl halides), and on the other hand dimethylamino-, diethylamino-, dibutylamino-, pyrrolidino-, piperidino-, and morpholino-ethyl chloride or -ethyl bromide, b -dimethylamino-, b -diethylamino-, b -piperidino-, b -morpholino-, g -dimethylamino-, g -diethylamino- and g -piperidino propyl chloride, b  - dimethylamino - isopropyl chloride, b  - dimethylamino-and b  - diethylamino - ethanol and -propanol, d -dimethyl (or diethyl)-amino- and d  - piperidino - n - butanol.  Examples describe the production of S-(b -diethylaminoethyl)-0.0 - diethyl - dithiophosphoric acid ester, diethyl - (b  - dimethylaminoethyl) - thiophosphoric acid ester, and diethyl-(d -dimethylaminobutyl)-thiophosphoric acid ester. Other ester products referred to are those of the above formula in which R1 and R2 are each ethyl radicals and -X-alkylene-Am is -S.CH2.CH2.N(CH3)2, -S-b -piperidinoethyl, -S-g -piperidinopropyl, -S-b  - morpholinoethyl, - -S-CH2.CH(CH3).N(CH3)2, -S.CH(CH3).CH2.N(CH3)2; -S-b -pyrrolidinoethyl, -O.CH2.CH2.N(C2H5)2, -O-b -piperidinoethyl, -O-g -dimethylaminopropyl, -O-b -piperidinopropyl, and -O-b -piperidino isopropyl.  The product in which R1 and R2 are C3H7 and X-alkylene-Am is -S-CH2.CH2.N(C2H5)2 is also referred to.  The products are stated to have pesticidal properties (see Group VI).ALSO:A composition for combatting insect pests, leaf aphids and red spider comprises a carrier or diluent and a basic thiophosphoric or dithiophosphoric acid ester having the formula:-(R1O)(R2O), PS (X-alkylene. Am) wherein R1 and R2 each represent an alkyl radical, X is sulphur or oxygen, alkylene represents an alkylene radical containing from 2 to 4 carbon atoms and Am is a dialkylamino, alkyleneimino, or morpholino radical (see Group IV(b)).  Specified alkyleneimino radicals are pyrrolidino and piperidino.  The carrier or diluent may be a pulverulent solid which may contain a wetting agent, or an inert organic liquid. Examples are given of (1) a dusting agent comprising b -diethylaminoethyl-diethyl thiophosphoric acid ester ground with talcum, and adhesive agent may also be added; (2) a wettable powder comprising S-(b -dimethylaminoethyl)-O.O-diethyl-dithiophosphoric acid ester and solid pulverised residue of sulphite waste liquor ground with a carrier such as chalk, kaolin or bentonite; the residue of the sulphite waste liquor can be replaced with the sodium salt of dibutylnaphthalene sulphonic acid and blood albumin; (3) an emulsion comprising S-(b -dimethylaminoethyl) - O, O - diethyl - dithiophosphoric acid ester dissolved in a solvent and mixed with an emulsifying agent.  Specified solvents are mixtures of benzene, toluene, xylene, acetone, low aliphatic alcohols, and petroleum distillates.  The emulsifying agents may be anion active, cation active, or non-ionogenic, examples being the sulphonates of fatty acid esters, the sulphonate of ricinoleic acid butyl ester, quaternary compounds, or condensation products of ethylene oxide with alkyl phenols or fatty alcohols.